US4089930A - Process for the catalytic reduction of nitric oxide - Google Patents
Process for the catalytic reduction of nitric oxide Download PDFInfo
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- US4089930A US4089930A US05/657,541 US65754176A US4089930A US 4089930 A US4089930 A US 4089930A US 65754176 A US65754176 A US 65754176A US 4089930 A US4089930 A US 4089930A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8621—Removing nitrogen compounds
- B01D53/8625—Nitrogen oxides
- B01D53/8628—Processes characterised by a specific catalyst
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
- Y02C20/00—Capture or disposal of greenhouse gases
- Y02C20/10—Capture or disposal of greenhouse gases of nitrous oxide (N2O)
Definitions
- Nitrogen oxides are undesirable products of reaction which result when carbonaceous fuels are burned such as in power plant operations.
- the gaseous effluent typically contains as the major source of pollutants sulfur oxides or sulfur dioxide and nitric oxides. It has been found possible to separate the sulfur dioxide from the effluent and to treat the sulfur dioxide separately. This results in an effluent primarily containing sulfur dioxide as less than 2000 ppm, nitric oxide, oxygen and nitrogen and water vapor.
- German Pat. No. 1,259,298 The use of a base metal catalyst to reduce nitric oxide to nitrogen with ammonia in the presence of oxygen and sulfur dioxide has been suggested, German Pat. No. 1,259,298.
- the catalyst life is limited and no controls are provided for the prevention of the formation of nitrous oxide and the exothermic reaction is difficult to control.
- a copper promoted catalyst on a catalytic support such as alumina, silica or diatomacous earth is suggested, U.S. Pat. No. 3,008,796.
- the reaction rates are not such that such a process would be considered economically possible for the treatment of a gaseous stream such as from a power plant emission.
- the elimination or inhibition of the formation of undesirable by-products is not controlled.
- the present invention is broadly directed to the catalytic reduction of nitric oxide to nitrogen with ammonia as a reductant. More particularly, the invention provides a high percent conversion of nitric oxide to nitrogen with ammonia while avoiding or minimizing the formation of undesirable by-products such as nitrous oxide.
- the invention is directed to the pretreatment of a base metal catalyst selected from the group consisting essentially of copper, iron, chromium, nickel, molybdenum, cobalt, vanadium, the lanthanides and the actinides or any combinations thereof with a nonmetallic element selected from Group VI A of the periodic system.
- the base metal catalysts copper, vanadium and iron either alone or any combination thereof are pretreated with a sulfur compound and/or selenium.
- the treated catalyst is then employed for the reduction of nitric oxide to nitrogen in a component system of ammonia, oxygen and an inert gas.
- both nitrogen and nitrous oxide are formed.
- nitric oxide oxygen and a controlled amount of sulfur dioxide using a base metal catalyst, the nitric oxide is reduced to nitrogen with substantially no nitrous oxide formation.
- the amount of sulfur dioxide in the system is unknown, either no sulfur dioxide or no controlled amount of sulfur dioxide, both nitrogen and nitrous oxide are formed.
- base metal catalysts are pretreated and for a system of nitric oxide and oxygen with ammonia using a base metal catalyst, substantially no nitrous oxide is formed.
- This pretreatment eliminates the necessity of controlling the amount of sulfur dioxide, if any, in the system to eliminate the undesirable by-product nitrous oxide when nitric oxide is reduced to nitrogen with ammonia using a base metal catalyst.
- the method of the invention broadly comprises pretreating a base metal catalyst from the group consisting essentially of ferric oxides, vanadium oxides and copper oxides by contacting the catalysts with a pretreatment stream comprising a vaporizable sulfur compound such as dimethyl sulfide, hydrogen sulfide, sulfur dioxide, carbon disulfide or elemental sulfur; or selenium to impregnate the catalyst.
- a vaporizable sulfur compound such as dimethyl sulfide, hydrogen sulfide, sulfur dioxide, carbon disulfide or elemental sulfur; or selenium to impregnate the catalyst.
- Ammonia is blended with a gaseous stream comprising nitric oxide and oxygen to form a blended stream which contacts the pretreated catalyst.
- the nitric oxide is reduced to nitrogen with substantially no nitrous oxide formation.
- the pretreatment stream preferably comprises H 2 or NH 3 .
- the pretreatment step is preferably conducted at temperatures between about 400° F. to 900° F.
- the time of pretreatment or exposure will depend upon the temperature used, and is generally between about 2 hours to 24 hours, preferably between 2 hours to 10 hours, the shorter duration at the higher temperatures.
- the composition of vaporizable sulfur compound or selenium compound in the pretreatment stream may be 0.5% to 10%, preferably 1% to 2%.
- FIG. 1 is a process flow diagram of the preferred embodiment of the invention.
- a power plant, 800 mw capacity, is shown at 10, and emits a flue gas stream at between about 200° F. to 1,000° F., preferably between 300° F. to 700° F., say for example at 500° F. and at a rate of approximately 200 ⁇ 10 6 cubic feet per hour.
- a representative composition of the flue gas is set forth below in Table I, it being understood that the composition will vary depending on operating conditions and the type of fuel being consumed.
- the remainder is comprised of N 2 & H 2 O.
- the stream is discharged from the power plant 10 having the above composition and is introduced to a precipitator 12 where approximately 95% of the fly ash is removed.
- the stream is discharged from the precipitator 12 less the removed fly ash, and ammonia from a source 14 is blended as a reductant gas with the stream to form a blended stream.
- This blended stream flows to a manifold 16 where it is introduced into a catalytic reactor 20 through a plurality of inlets 18a-d.
- the ammonia flow rate is dependant on the ammonia-nitric oxide ratio.
- Table II lists a range of mole ratios and the associated amount of ammonia available for the subsequent catalytic reaction.
- the catalytic reactor comprises a plurality of catalytic beds 22a--d.
- the streams introduced flow through the catalytic beds where the following reaction primarily occurs.
- Table III sets forth the cubic footage requirements of the catalytic bed in reference to the space velocity.
- the catalyst employed in this particular embodiment is 10% V 2 O 5 on alumina such as available from Harshaw Chemical and designated VO301, which has been pretreated.
- the percent reduction of nitric oxide in the blended stream under the conditions set forth herein exceeds 80% and may be approximately 100% with no nitrous oxide formation.
- a representative composition discharged from the catalytic reactor 20 through outlets 24a-d and through manifold 26 is set forth in Table IV.
- the V 2 O 5 on alumina is pretreated to ensure that there is substantially no nitrous oxide formed, whether or not there is sulfur dioxide present in the stream.
- the catalyst is contacted with a stream of 2% dimethyl sulfide and 2% hydrogen in helium at a temperature of between about 500° to 700° F., say for example 600° F., for a period of between about 4 to 8 hours, say for example 6 hours. After pretreatment, the catalyst is placed on supports for the beds 22a--d.
- base metal catalysts which may be similarly pretreated are copper, iron, chromium, nickel, molybdenum, cobalt, or appropriate combinations thereof, normally supported on a high surface area material such as alumina, silica alumina, or zeolites.
- the invention may be utilized for NO removal from the exhaust of a turbine generator employing equipment functionally equivalent to that shown in the drawing.
- a turbine generator with a capacity of about 20 mw discharges an exhaust of about 30 ⁇ 10 5 cubic feet per hour.
- a representative composition of the exhaust is set forth below in Table V, it being understood that the composition will vary depending upon operating conditions and the type of fuel being consumed.
- the stream discharged from the generator, having the above composition, is introduced into a catalytic reactor substantially identical to that shown in the drawing and described in reference to the preferred embodiment of the invention.
- the catalytic reactor includes a plurality of catalytic beds in a column-like configuration disposed in a plurality of zones.
- a reductant gas more particularly, ammonia
- ammonia is blended with the exhaust gas stream and introduced through a manifold to a catalytic reactor at a temperature of between about 500° F. to 900° F., say for example 800° F.
- the ammonia-nitric oxide molar ratio may vary between 0.7 to 1.0.
- Table VI lists the mole ratios and required amount of ammonia necessary for the subsequent catalytic reaction.
- the total catalytic volume is dependent upon the space velocity.
- Table VII sets forth the cubic footage requirements of the catalyst in reference to space velocity, which varies between about 25,000 hr -1 to 100,000 hr -1 .
- the catalyst employed in this alternative embodiment is V 2 O 5 supported on alumina, which is pretreated as described in the preferred embodiment.
- the percent reduction of nitric oxide under the conditions set forth herein is substantially 100% with substantially no nitrous oxide formation.
- a representative composition discharged from the catalytic reactor is set forth below in Table VIII.
- Example 1 The catalysts of Example 1 were tested in a similar fashion, except approximately 2000 ppm of sulfur dioxide was added to the feed mixture of Example 1. The results obtained are set forth in Table XI. It can be seen from the table that the addition of sulfur dioxide to the feed of the non-noble metal catalysts has reduced the undesirable formation of N 2 O to zero, with N 2 being the only reaction product in these cases. The addition of sulfur dioxide did not inhibit the formation of N 2 O for the platinum catalyst however.
- Example 1 The catalysts of Example 1 were exposed to a stream of 2% dimethyl sulfide and 2% H 2 in helium for 6 hours at 600° F., and were tested at the conditions of Example 1 with no sulfur dioxide added to the feed to the reactors. Substantially no production of N 2 O was observed for the non-noble metal catalysts, with the only reaction product being N 2 and the downstream concentration of No and N 2 O being substantially the same as in Table XI. This pretreatment with dimethyl sulfide did not inhibit N 2 O formation with the platinum catalyst.
- nitrous oxide formation is prevented whether or not sulfur dioxide is present in the stream containing the nitric oxide.
- My invention eliminates the requirement of controlling the amount of SO 2 remaining as a flue gas stream for the reduction of nitric oxide without nitrous oxide formation.
Abstract
Base metal catalysts are pretreated with selenium, sulfur or sulfur compounds. Subsequently, a gaseous stream comprising nitric oxide, oxygen and ammonia is passed over the pretreated catalysts. The nitric oxide is reduced to nitrogen and no nitrous oxide is formed.
Description
Nitrogen oxides, particularly nitric oxide, are undesirable products of reaction which result when carbonaceous fuels are burned such as in power plant operations.
Various techniques have been proposed for removing nitric oxides from gaseous streams to prevent pollution of the atmosphere, such as absorption, scrubbing and catalytic conversion.
Catalytic reduction of nitric oxides with ammonia or hydrogen in the presence of nickel and oxides of iron and chromium has been proposed (U.S. Pat. No. 2,381,696; U.S. Pat. No. 3,008,796; and German Pat. No. 1,259,298). The reaction is exothermic and control of the temperature in the catalyst bed is difficult, so that combustion of the ammonia is likely to occur.
Removal of nitric oxides from tail gas streams of nitric acid plants has been attempted by reaction with ammonia, hydrogen, or methane over a catalyst consisting of a supported metal of the platinum group. Anderson et al, Ind. Eng. Chem. Vol. 53, p. 199 (1961); and Adlhart et al, Chem. Eng. Progra. Vol. 67, p. 73-78 (1971). With this method there has been difficulty with control of the exothermic reaction, which results in pressure surges and overheating of the reactor. Also, in some instances, hydrogen cyanide is produced as a by-product.
In power plant emissions, the gaseous effluent typically contains as the major source of pollutants sulfur oxides or sulfur dioxide and nitric oxides. It has been found possible to separate the sulfur dioxide from the effluent and to treat the sulfur dioxide separately. This results in an effluent primarily containing sulfur dioxide as less than 2000 ppm, nitric oxide, oxygen and nitrogen and water vapor.
The prior art methods for catalytically reducing nitric oxide with ammonia as a reducing gas experience problems with the temperature of operation required to maintain the efficiency of the catalyst employed, deterioration of the catalyst, controlling exothermic reactions and preventing the formation of by-products which are pollutants, particularly nitrous oxide.
The use of a base metal catalyst to reduce nitric oxide to nitrogen with ammonia in the presence of oxygen and sulfur dioxide has been suggested, German Pat. No. 1,259,298. However, the catalyst life is limited and no controls are provided for the prevention of the formation of nitrous oxide and the exothermic reaction is difficult to control. Further, in similar component systems for the reduction of nitric oxide to nitrogen with ammonia, the use of a copper promoted catalyst on a catalytic support such as alumina, silica or diatomacous earth is suggested, U.S. Pat. No. 3,008,796. The reaction rates are not such that such a process would be considered economically possible for the treatment of a gaseous stream such as from a power plant emission. The elimination or inhibition of the formation of undesirable by-products is not controlled.
The present invention is broadly directed to the catalytic reduction of nitric oxide to nitrogen with ammonia as a reductant. More particularly, the invention provides a high percent conversion of nitric oxide to nitrogen with ammonia while avoiding or minimizing the formation of undesirable by-products such as nitrous oxide. The invention is directed to the pretreatment of a base metal catalyst selected from the group consisting essentially of copper, iron, chromium, nickel, molybdenum, cobalt, vanadium, the lanthanides and the actinides or any combinations thereof with a nonmetallic element selected from Group VI A of the periodic system.
In a preferred embodiment, the base metal catalysts copper, vanadium and iron either alone or any combination thereof are pretreated with a sulfur compound and/or selenium. The treated catalyst is then employed for the reduction of nitric oxide to nitrogen in a component system of ammonia, oxygen and an inert gas.
In the catalytic reduction of nitric oxide to nitrogen in a multi-component system of nitric oxide, oxygen, ammonia and an inert gas several reactions are believed to occur. The more important reactions are:
6NO + 4NH.sub.3 → 5N.sub.2 + 6H.sub.2 O
16no + 4nh.sub.3 → 1on.sub.2 o + 6h.sub.2 o
3o.sub.2 + 4nh.sub.3 → 2n.sub.2 + 6h.sub.2 o
4o.sub.2 + 4nh.sub.3 → 2n.sub.2 o + 6h.sub.2 o
5o.sub.2 + 4nh.sub.3 → 4no + 6h.sub.2 o
in a system of nitric oxide and oxygen with ammonia, to reduce the nitric oxide with or without sulfur dioxide added, using a noble metal catalyst, both nitrogen and nitrous oxide are formed.
In a system of nitric oxide, oxygen and a controlled amount of sulfur dioxide using a base metal catalyst, the nitric oxide is reduced to nitrogen with substantially no nitrous oxide formation. Where the amount of sulfur dioxide in the system is unknown, either no sulfur dioxide or no controlled amount of sulfur dioxide, both nitrogen and nitrous oxide are formed.
In the present invention, base metal catalysts are pretreated and for a system of nitric oxide and oxygen with ammonia using a base metal catalyst, substantially no nitrous oxide is formed. This pretreatment eliminates the necessity of controlling the amount of sulfur dioxide, if any, in the system to eliminate the undesirable by-product nitrous oxide when nitric oxide is reduced to nitrogen with ammonia using a base metal catalyst.
The method of the invention broadly comprises pretreating a base metal catalyst from the group consisting essentially of ferric oxides, vanadium oxides and copper oxides by contacting the catalysts with a pretreatment stream comprising a vaporizable sulfur compound such as dimethyl sulfide, hydrogen sulfide, sulfur dioxide, carbon disulfide or elemental sulfur; or selenium to impregnate the catalyst. Ammonia is blended with a gaseous stream comprising nitric oxide and oxygen to form a blended stream which contacts the pretreated catalyst. The nitric oxide is reduced to nitrogen with substantially no nitrous oxide formation. To promote the formation of metal sulfides on the catalyst or the deposition of sulfur, the pretreatment stream preferably comprises H2 or NH3. The pretreatment step is preferably conducted at temperatures between about 400° F. to 900° F. The time of pretreatment or exposure will depend upon the temperature used, and is generally between about 2 hours to 24 hours, preferably between 2 hours to 10 hours, the shorter duration at the higher temperatures. The composition of vaporizable sulfur compound or selenium compound in the pretreatment stream may be 0.5% to 10%, preferably 1% to 2%.
FIG. 1 is a process flow diagram of the preferred embodiment of the invention.
A power plant, 800 mw capacity, is shown at 10, and emits a flue gas stream at between about 200° F. to 1,000° F., preferably between 300° F. to 700° F., say for example at 500° F. and at a rate of approximately 200 × 106 cubic feet per hour. A representative composition of the flue gas is set forth below in Table I, it being understood that the composition will vary depending on operating conditions and the type of fuel being consumed.
TABLE I ______________________________________ Comp. of Flue Gas Comp. Vol. % lb/hr ______________________________________ CO.sub.2 14.5 1.512 × 10.sup.6 O.sub.2 3.0 2.275 × 10.sup.5 SO.sub.2 0.2 3.039 × 10.sup.4 NO.sub.x 0.075 5.329 × 10.sup.3 Fly Ash 0.2 -- ______________________________________ The remainder is comprised of N.sub.2 & H.sub.2 O.
The remainder is comprised of N2 & H2 O.
The stream is discharged from the power plant 10 having the above composition and is introduced to a precipitator 12 where approximately 95% of the fly ash is removed. The stream is discharged from the precipitator 12 less the removed fly ash, and ammonia from a source 14 is blended as a reductant gas with the stream to form a blended stream. This blended stream flows to a manifold 16 where it is introduced into a catalytic reactor 20 through a plurality of inlets 18a-d. The ammonia flow rate is dependant on the ammonia-nitric oxide ratio. For this example, Table II lists a range of mole ratios and the associated amount of ammonia available for the subsequent catalytic reaction.
TABLE II
______________________________________
NH.sub.3 /NO mole ratio
lb NH.sub.3 /hr.
______________________________________
0.7 2115.5
0.8 2417.7
0.9 2720.0
1.0 3022.1
______________________________________
The catalytic reactor comprises a plurality of catalytic beds 22a--d. The streams introduced flow through the catalytic beds where the following reaction primarily occurs.
6NO + 4NH.sub.3 → 5N.sub.2 + 6H.sub.2 O
the catalyst volume is dependent upon the space velocity. Table III sets forth the cubic footage requirements of the catalytic bed in reference to the space velocity.
TABLE III ______________________________________ Space velocity hr.sup.-1 reactor Catalyst conditions vol., ft.sup.3 ______________________________________ 25,000 8376.9 50,000 4188.5 75,000 2792.3 100,000 2094.2 ______________________________________
The catalyst employed in this particular embodiment is 10% V2 O5 on alumina such as available from Harshaw Chemical and designated VO301, which has been pretreated. The percent reduction of nitric oxide in the blended stream under the conditions set forth herein exceeds 80% and may be approximately 100% with no nitrous oxide formation. A representative composition discharged from the catalytic reactor 20 through outlets 24a-d and through manifold 26 is set forth in Table IV.
TABLE IV ______________________________________ Comp. of Reactor Exit Gas (after electrostatic precipitation) Comp. Vol. % ______________________________________ CO.sub.2 14.5 O.sub.2 2.9 SO.sub.2 0.2 NO.sub.x 0.020 Fly Ash 0.01 ______________________________________
This reduced stream at between about 300° to 700° F., say for example 500° F., is introduced into a heat exchanger 18 where it is cooled by incoming air to about 350° F. It is then discharged to the stack by a conventional fan 30.
The V2 O5 on alumina is pretreated to ensure that there is substantially no nitrous oxide formed, whether or not there is sulfur dioxide present in the stream. The catalyst is contacted with a stream of 2% dimethyl sulfide and 2% hydrogen in helium at a temperature of between about 500° to 700° F., say for example 600° F., for a period of between about 4 to 8 hours, say for example 6 hours. After pretreatment, the catalyst is placed on supports for the beds 22a--d.
Other base metal catalysts which may be similarly pretreated are copper, iron, chromium, nickel, molybdenum, cobalt, or appropriate combinations thereof, normally supported on a high surface area material such as alumina, silica alumina, or zeolites.
In the pretreatment of the catalyst, other suitable compounds which may be used include hydrogen sulfide, sulfur dioxide, carbon disulfide or elemental sulfur; or selenium at operating conditions similar to those set forth above.
In an alternative embodiment, the invention may be utilized for NO removal from the exhaust of a turbine generator employing equipment functionally equivalent to that shown in the drawing. A turbine generator with a capacity of about 20 mw discharges an exhaust of about 30 × 105 cubic feet per hour. A representative composition of the exhaust is set forth below in Table V, it being understood that the composition will vary depending upon operating conditions and the type of fuel being consumed.
TABLE V
______________________________________
Comp. of Exhaust Gas
Composition Vol. Frac. lb/hr
______________________________________
O.sub.2 .16 16.42 × 10.sup.6
SO.sub.x 28 × 10.sup.-6
57.30
NO 114 × 10.sup.-6
107.6
CO 5 × 10.sup.-6
4.397
______________________________________
The stream discharged from the generator, having the above composition, is introduced into a catalytic reactor substantially identical to that shown in the drawing and described in reference to the preferred embodiment of the invention. More particularly, the catalytic reactor includes a plurality of catalytic beds in a column-like configuration disposed in a plurality of zones. A reductant gas, more particularly, ammonia, is blended with the exhaust gas stream and introduced through a manifold to a catalytic reactor at a temperature of between about 500° F. to 900° F., say for example 800° F. The ammonia-nitric oxide molar ratio may vary between 0.7 to 1.0. The following Table VI lists the mole ratios and required amount of ammonia necessary for the subsequent catalytic reaction.
TABLE VI ______________________________________ NH.sub.3 /NO Mole Ratio lb. NH.sub.3 /hr ______________________________________ 0.7 42.72 0.8 48.82 0.9 54.93 1.0 61.03 ______________________________________
The total catalytic volume is dependent upon the space velocity. The following Table VII sets forth the cubic footage requirements of the catalyst in reference to space velocity, which varies between about 25,000 hr-1 to 100,000 hr-1.
TABLE VII
______________________________________
Space Vel. Hr.sup.-1
Catalyst Vol.
Reactor Cond. Ft..sup.3
______________________________________
25,000 1257.
50,000 628.4
75,000 418.9
100,000 314.2
______________________________________
The catalyst employed in this alternative embodiment is V2 O5 supported on alumina, which is pretreated as described in the preferred embodiment. The percent reduction of nitric oxide under the conditions set forth herein is substantially 100% with substantially no nitrous oxide formation. A representative composition discharged from the catalytic reactor is set forth below in Table VIII.
TABLE VIII ______________________________________ Comp. of Reactor Exit Gas Composition Vol. Frac. ______________________________________ O.sub.2 .15 SO.sub.x 28 × 10.sup.-6 NO 50 × 10.sup.-6 CO 5 × 10.sup.-6 ______________________________________
The following examples illustrate the suitability of the catalyst compositions when used in the inventive process.
Samples of six commercially available catalysts were used as received to reduce nitric oxide by ammonia in the absence of sulfur dioxide, as set forth in Table IX below.
TABLE IX
______________________________________
Catalyst Type Manufacturer Identification
______________________________________
10% CuO on alumina
Harshaw Cu0803
Cr promoted iron oxide
Girdler G3A
Copper chromite Girdler G13
3% Pt on alumina
Matthey Bishop
MB30
10% V.sub.2 O.sub.5 on alumina
Harshaw VO301
10% V.sub.2 O.sub.5 on silica alumina
Harshaw VO701
______________________________________
Approximately 3 grams of each catalyst was changed to individual 1/4 inch diameter aluminum reactors and placed in a furnace such as a Lindberg Heavi-Duty furnace. A feed mixture comprising approximately 520 ppm NH3, 600 ppm NO, 5000 ppm O2, and the balance He was passed over these catalysts at a space velocity of 380 std. cc/gm-min. The results are set forth in Table X.
By comparison to the inlet NO level, it can be seen that substantial quantities of NO have been converted, but that the bulk of it has been converted to N2 O, an undesirable by-product, rather than to N2, the desired product.
The catalysts of Example 1 were tested in a similar fashion, except approximately 2000 ppm of sulfur dioxide was added to the feed mixture of Example 1. The results obtained are set forth in Table XI. It can be seen from the table that the addition of sulfur dioxide to the feed of the non-noble metal catalysts has reduced the undesirable formation of N2 O to zero, with N2 being the only reaction product in these cases. The addition of sulfur dioxide did not inhibit the formation of N2 O for the platinum catalyst however.
TABLE X
______________________________________
PPM
Product Gas
Composition
Catalyst Type Temperature, ° F
NO N.sub.2 O
______________________________________
3% Pt on alumina
431 11 392
3% Pt on alumina
457 10 405
3% Pt on alumina
506 46 374
3% Pt on alumina
557 79 353
10% CuO on alumina
430 79 119
10% CuO on alumina
457 81 153
10% CuO on alumina
507 119 252
10% CuO on alumina
556 139 331
Copper chromite 430 181 108
Copper chromite 458 149 131
Copper chromite 507 187 194
Copper chromite 557 258 275
Cr promoted iron oxide
433 175 153
Cr promoted iron oxide
460 203 267
Cr promoted iron oxide
509 219 297
Cr promoted iron oxide
559 220 301
10% V.sub.2 O.sub.5 on alumina
432 44 55
10% V.sub.2 O.sub.5 on alumina
459 59 86
10% V.sub.2 O.sub.5 on alumina
508 70 42
10% V.sub.2 O.sub.5 on alumina
559 222 322
10% V.sub.2 O.sub.5 on silica alumina
433 220 59
10% V.sub.2 O.sub.5 on silica alumina
460 140 106
10% V.sub.2 O.sub.5 on silica alumina
508 83 93
10% V.sub.2 O.sub.5 on silica alumina
560 197 279
______________________________________
TABLE XI
______________________________________
Temper- Down-
ature stream Concentration
Catalyst Type ° F
NO N.sub.2 O
______________________________________
3% Pt on alumina
457 165 419
3% Pt on alumina
506 131 404
3% Pt on alumina
553 143 449
10% CuO on alumina
455 455 0
10% CuO on alumina
505 342 0
10% CuO on alumina
557 91 0
Copper chromite 455 534 0
Copper chromite 506 477 0
Copper chromite 553 415 0
Cr promoted iron oxide
457 470 0
Cr promoted iron oxide
507 273 0
Cr promoted iron oxide
559 29 0
10% V.sub.2 O.sub.5 on alumina
458 63 0
10% V.sub.2 O.sub.5 on alumina
508 0 0
10% V.sub.2 O.sub.5 on alumina
560 0 0
10% V.sub.2 O.sub.5 on silica alumina
459 155 0
10% V.sub.2 O.sub.5 on silica alumina
510 19 0
10% V.sub.2 O.sub.5 on silica alumina
561 0 0
______________________________________
The catalysts of Example 1 were exposed to a stream of 2% dimethyl sulfide and 2% H2 in helium for 6 hours at 600° F., and were tested at the conditions of Example 1 with no sulfur dioxide added to the feed to the reactors. Substantially no production of N2 O was observed for the non-noble metal catalysts, with the only reaction product being N2 and the downstream concentration of No and N2 O being substantially the same as in Table XI. This pretreatment with dimethyl sulfide did not inhibit N2 O formation with the platinum catalyst.
By pretreating the catalysts with the sulfur or selenium compounds, nitrous oxide formation is prevented whether or not sulfur dioxide is present in the stream containing the nitric oxide. My invention eliminates the requirement of controlling the amount of SO2 remaining as a flue gas stream for the reduction of nitric oxide without nitrous oxide formation.
Claims (7)
1. A method for the catalytic reduction of nitric oxide which includes:
(a) blending ammonia with a gaseous stream comprising nitric oxide and oxygen, the ammonia added in an amount sufficient to react with the total amount of nitric oxide in the stream to form a blended stream;
(b) placing the blended stream of step (a) in catalytic contact with a pretreated base metal catalyst at a temperature between about 300° F.-700° F. to reduce the nitric oxide to nitrogen while preventing the formation of nitrous oxide, the catalyst selected from the group consisting of copper, vanadium, iron and molybdenum and combinations thereof which catalyst has been contacted with a compound selected from the group consisting of sulfur, dimethyl sulfide, hydrogen sulfide and carbon disulfide and combinations thereof at a temperature of between about 400° F.-900° F. to form the pretreated catalyst.
2. A method of claim 1 wherein the catalyst is vanadium.
3. The method of claim 1 wherein the catalyst is chromium promoted iron oxide.
4. The method of claim 1 wherein the catalyst is copper.
5. The method of claim 1 which includes reducing at least ninety percent of the nitric oxide while preventing the formation of nitrous oxide.
6. The method of claim 1 wherein the catalyst is pretreated with a pretreatment stream of 2% dimethyl sulfide and 2% hydrogen in helium.
7. The method of claim 1, wherein the base metal catalyst pretreated is selected from the group consisting of copper, vanadium and iron.
Priority Applications (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US05/657,541 US4089930A (en) | 1976-02-12 | 1976-02-12 | Process for the catalytic reduction of nitric oxide |
| JP1314277A JPS52113365A (en) | 1976-02-12 | 1977-02-10 | Nitric oxide catalytic reduction |
| DE19772705818 DE2705818A1 (en) | 1976-02-12 | 1977-02-11 | METHOD FOR CATALYTIC REDUCTION OF NITROGEN OXIDE |
| US05/786,144 US4080426A (en) | 1976-02-12 | 1977-04-11 | Reduction of nitric oxide using catalysts pretreated with selenium |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US05/657,541 US4089930A (en) | 1976-02-12 | 1976-02-12 | Process for the catalytic reduction of nitric oxide |
Related Child Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US05/786,144 Division US4080426A (en) | 1976-02-12 | 1977-04-11 | Reduction of nitric oxide using catalysts pretreated with selenium |
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| Publication Number | Publication Date |
|---|---|
| US4089930A true US4089930A (en) | 1978-05-16 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US05/657,541 Expired - Lifetime US4089930A (en) | 1976-02-12 | 1976-02-12 | Process for the catalytic reduction of nitric oxide |
| US05/786,144 Expired - Lifetime US4080426A (en) | 1976-02-12 | 1977-04-11 | Reduction of nitric oxide using catalysts pretreated with selenium |
Family Applications After (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US05/786,144 Expired - Lifetime US4080426A (en) | 1976-02-12 | 1977-04-11 | Reduction of nitric oxide using catalysts pretreated with selenium |
Country Status (3)
| Country | Link |
|---|---|
| US (2) | US4089930A (en) |
| JP (1) | JPS52113365A (en) |
| DE (1) | DE2705818A1 (en) |
Cited By (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4212852A (en) * | 1977-05-06 | 1980-07-15 | Takeda Chemical Industries, Ltd. | Method of deodorizing gas containing hydrogen sulfide and ammonia and/or amines |
| US4246234A (en) * | 1978-05-26 | 1981-01-20 | New England Power Service Company | Method and apparatus for reducing nitric oxide |
| US4590174A (en) * | 1983-07-26 | 1986-05-20 | Phillips Petroleum Company | Olefin metathesis catalyst |
| US4847054A (en) * | 1986-12-06 | 1989-07-11 | Metallgesellschaft Ag | Process for catalytically reducing NO contained in a gas |
| US4943547A (en) * | 1988-09-13 | 1990-07-24 | Seamans James D | Method of presulfiding a hydrotreating catalyst |
| US5030436A (en) * | 1989-05-03 | 1991-07-09 | Ethyl Corporation | Spent acid purification process |
| US5041404A (en) * | 1988-09-13 | 1991-08-20 | Cri Ventures, Inc. | Method of presulfiding a hydrotreating, hydrocracking or tail gas treating catalyst |
| US5106602A (en) * | 1990-07-03 | 1992-04-21 | The Research Foundation Of State University Of New York | Low temperature catalytic reduction of nitrogen oxides |
| US5120516A (en) * | 1990-01-08 | 1992-06-09 | Physical Sciences, Inc. | Process for removing nox emissions from combustion effluents |
| US5215954A (en) * | 1991-07-30 | 1993-06-01 | Cri International, Inc. | Method of presulfurizing a hydrotreating, hydrocracking or tail gas treating catalyst |
| US5681787A (en) * | 1993-05-04 | 1997-10-28 | Cri International, Inc. | Method of treating spontaneously combustible catalysts |
| US5786293A (en) * | 1996-06-17 | 1998-07-28 | Shell Oil Company | Process for presulfiding hydrocarbon processing catalysts |
| US5821191A (en) * | 1996-06-17 | 1998-10-13 | Shell Oil Company | Process for presulfiding hydrocarbon processing catalysts |
| US6093309A (en) * | 1993-05-04 | 2000-07-25 | Cri International, Inc. | Method of treating spontaneously combustible catalysts |
| US6291391B1 (en) | 1998-11-12 | 2001-09-18 | Ifp North America, Inc. | Method for presulfiding and preconditioning of residuum hydroconversion catalyst |
| CN1107707C (en) * | 1999-01-25 | 2003-05-07 | 中国石油化工集团公司 | Process for presulfurizing hydrocatalyst |
| US20110017641A1 (en) * | 2009-07-24 | 2011-01-27 | Lummus Technology Inc. | Pre-sulfiding and pre-conditioning of residuum hydroconversion catalysts for ebullated-bed hydroconversion processes |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4295998A (en) * | 1980-03-14 | 1981-10-20 | Phillips Petroleum Company | Selenium or tellurium treated silica |
| US4331789A (en) * | 1980-03-14 | 1982-05-25 | Phillips Petroleum Company | Polymerization using a selenium or tellurium treated catalyst |
| US5139756A (en) * | 1989-10-05 | 1992-08-18 | Nkk Corporation | Catalytic oxidation of ammonia |
| FI98926C (en) * | 1994-10-05 | 1997-09-10 | Valtion Teknillinen | Process for removing ammonia from gasification gas |
| US20100269492A1 (en) * | 2009-04-27 | 2010-10-28 | Tenneco Automotive Operating Company Inc. | Diesel aftertreatment system |
| CN111450698B (en) * | 2020-04-09 | 2022-05-27 | 山东迅达化工集团有限公司 | Selective oxidation purification treatment method for ammonia-containing gas flow |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3563912A (en) * | 1968-03-14 | 1971-02-16 | Union Oil Co | Catalyst composition and sulfiding method |
| DE2411888A1 (en) * | 1973-03-13 | 1974-09-26 | Agency Ind Science Techn | Catalyst for redn. of nitrogen oxides in effluent gases - using gaseous ammonia, comprises metal oxide on activated alumina |
| US3850846A (en) * | 1973-04-19 | 1974-11-26 | Texaco Inc | Catalyst sulfiding procedure |
| US3857921A (en) * | 1972-09-27 | 1974-12-31 | Asahi Chemical Ind | Method for eliminating nitrogen oxides and catalyst composition for use in practicing said method |
| US3864451A (en) * | 1973-08-16 | 1975-02-04 | Environics Inc | Method for Removing Nitric Oxide from Combustion Gases |
| US3914390A (en) * | 1972-09-20 | 1975-10-21 | Hitachi Ltd | Method for reducing nitrogen oxides |
| US3933979A (en) * | 1972-09-22 | 1976-01-20 | Metallgesellschaft Aktiengesellschaft | Gas purifying method |
| US3981971A (en) * | 1973-09-13 | 1976-09-21 | Kurashiki Boseki Kabushiki Kaisha | Process for reducing nitrogen oxides |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR1271524A (en) * | 1960-06-14 | 1961-09-15 | Engelhard Ind Inc | Treatment of gases containing nitrogen oxides and oxygen |
| JPS5410944B2 (en) * | 1973-08-27 | 1979-05-10 | ||
| US4002723A (en) * | 1973-09-29 | 1977-01-11 | Hitachi Shipbuilding And Engineering Co., Ltd. | Method of removal of nitrogen oxides |
| JPS50108167A (en) * | 1974-02-01 | 1975-08-26 | ||
| US4043939A (en) * | 1975-10-10 | 1977-08-23 | Kurashiki Boseki Kabushiki Kaisha | Reactivation of catalysts useful for nitrogen oxide removal |
-
1976
- 1976-02-12 US US05/657,541 patent/US4089930A/en not_active Expired - Lifetime
-
1977
- 1977-02-10 JP JP1314277A patent/JPS52113365A/en active Pending
- 1977-02-11 DE DE19772705818 patent/DE2705818A1/en not_active Withdrawn
- 1977-04-11 US US05/786,144 patent/US4080426A/en not_active Expired - Lifetime
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3563912A (en) * | 1968-03-14 | 1971-02-16 | Union Oil Co | Catalyst composition and sulfiding method |
| US3914390A (en) * | 1972-09-20 | 1975-10-21 | Hitachi Ltd | Method for reducing nitrogen oxides |
| US3933979A (en) * | 1972-09-22 | 1976-01-20 | Metallgesellschaft Aktiengesellschaft | Gas purifying method |
| US3857921A (en) * | 1972-09-27 | 1974-12-31 | Asahi Chemical Ind | Method for eliminating nitrogen oxides and catalyst composition for use in practicing said method |
| DE2411888A1 (en) * | 1973-03-13 | 1974-09-26 | Agency Ind Science Techn | Catalyst for redn. of nitrogen oxides in effluent gases - using gaseous ammonia, comprises metal oxide on activated alumina |
| US3850846A (en) * | 1973-04-19 | 1974-11-26 | Texaco Inc | Catalyst sulfiding procedure |
| US3864451A (en) * | 1973-08-16 | 1975-02-04 | Environics Inc | Method for Removing Nitric Oxide from Combustion Gases |
| US3981971A (en) * | 1973-09-13 | 1976-09-21 | Kurashiki Boseki Kabushiki Kaisha | Process for reducing nitrogen oxides |
Non-Patent Citations (1)
| Title |
|---|
| Chemical Abstracts, vol. 84, 1976, 84:34895v; 84:21719r. * |
Cited By (24)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4212852A (en) * | 1977-05-06 | 1980-07-15 | Takeda Chemical Industries, Ltd. | Method of deodorizing gas containing hydrogen sulfide and ammonia and/or amines |
| US4246234A (en) * | 1978-05-26 | 1981-01-20 | New England Power Service Company | Method and apparatus for reducing nitric oxide |
| US4590174A (en) * | 1983-07-26 | 1986-05-20 | Phillips Petroleum Company | Olefin metathesis catalyst |
| US4847054A (en) * | 1986-12-06 | 1989-07-11 | Metallgesellschaft Ag | Process for catalytically reducing NO contained in a gas |
| US5041404A (en) * | 1988-09-13 | 1991-08-20 | Cri Ventures, Inc. | Method of presulfiding a hydrotreating, hydrocracking or tail gas treating catalyst |
| US4943547A (en) * | 1988-09-13 | 1990-07-24 | Seamans James D | Method of presulfiding a hydrotreating catalyst |
| US5030436A (en) * | 1989-05-03 | 1991-07-09 | Ethyl Corporation | Spent acid purification process |
| US5120516A (en) * | 1990-01-08 | 1992-06-09 | Physical Sciences, Inc. | Process for removing nox emissions from combustion effluents |
| US5106602A (en) * | 1990-07-03 | 1992-04-21 | The Research Foundation Of State University Of New York | Low temperature catalytic reduction of nitrogen oxides |
| US5688736A (en) * | 1991-07-30 | 1997-11-18 | Cri International, Inc. | Method of presulfurizing a hydrotreating, hydrocracking or tail gas treating catalyst |
| US5215954A (en) * | 1991-07-30 | 1993-06-01 | Cri International, Inc. | Method of presulfurizing a hydrotreating, hydrocracking or tail gas treating catalyst |
| US5292702A (en) * | 1991-07-30 | 1994-03-08 | Cri International, Inc. | Presulfurized hydrotreating, hydrocracking or tail gas treating catalyst |
| US5468372A (en) * | 1991-07-30 | 1995-11-21 | Shell Oil Company | Process of hydrotreating and/or hydrocracking hydrocarbon streams or tail gas treating sulfur-containing gas streams |
| US5681787A (en) * | 1993-05-04 | 1997-10-28 | Cri International, Inc. | Method of treating spontaneously combustible catalysts |
| US5990037A (en) * | 1993-05-04 | 1999-11-23 | Cri International, Inc. | Method of treating spontaneously combustible catalysts |
| US6077807A (en) * | 1993-05-04 | 2000-06-20 | Cri International, Inc. | Method of treating spontaneously combustible catalysts |
| US6093309A (en) * | 1993-05-04 | 2000-07-25 | Cri International, Inc. | Method of treating spontaneously combustible catalysts |
| US5786293A (en) * | 1996-06-17 | 1998-07-28 | Shell Oil Company | Process for presulfiding hydrocarbon processing catalysts |
| US5821191A (en) * | 1996-06-17 | 1998-10-13 | Shell Oil Company | Process for presulfiding hydrocarbon processing catalysts |
| US6291391B1 (en) | 1998-11-12 | 2001-09-18 | Ifp North America, Inc. | Method for presulfiding and preconditioning of residuum hydroconversion catalyst |
| CN1107707C (en) * | 1999-01-25 | 2003-05-07 | 中国石油化工集团公司 | Process for presulfurizing hydrocatalyst |
| US20110017641A1 (en) * | 2009-07-24 | 2011-01-27 | Lummus Technology Inc. | Pre-sulfiding and pre-conditioning of residuum hydroconversion catalysts for ebullated-bed hydroconversion processes |
| WO2011011200A2 (en) | 2009-07-24 | 2011-01-27 | Lummus Technology Inc. | Pre-sulfiding and pre-conditioning of residuum hydroconversion catalysts for ebullated-bed hydroconversion processes |
| US9523048B2 (en) | 2009-07-24 | 2016-12-20 | Lummus Technology Inc. | Pre-sulfiding and pre-conditioning of residuum hydroconversion catalysts for ebullated-bed hydroconversion processes |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS52113365A (en) | 1977-09-22 |
| DE2705818A1 (en) | 1977-08-25 |
| US4080426A (en) | 1978-03-21 |
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